JPH06135748A - Intermediate film for laminated glass and laminated glass using the same - Google Patents

Abstract

PURPOSE:To obtain an intermediate film for laminated glass and to obtain laminated glass which prevents reduction of sound insulation effect due to coincidence effect and stably maintains sound insulating performance for a long time without decreasing good characteristics of a plasticized polyvinylacetal resin intermediate film. CONSTITUTION:The intermediate film is obtd. by laminating a resin film A and a resin film B. The resin film A consists of a plasticizer and polyvinylacetal resin obtd. by producing acetal of polyvinylalcohol having <=93mol% saponification degree with aldehyde having 1-4 carbon number. The resin film B consists of a plasticizer and polyvinylacetal resin obtd. by producing acetal of polyvinylalcohol of >=98mol% saponification degree with aldehyde having 1-4 carbon number. In this case, the amt. of the plasticizer in the resin film A is larger than the amt. of the plasticizer in the resin film B, or the resin film A and resin film B are adhered with a transparent film which does not permeate the plasticizer. By using this intermediate film, a sound-insulating laminated glass of the purpose is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer film for laminated glass having excellent sound insulation and a laminated glass using the same.

[0002]

2. Description of the Related Art Laminated glass in which an interlayer film made of a plasticized polyvinyl butyral resin is adhered between two transparent glass plates is widely used, for example, as window glass for automobiles and buildings.

As such an interlayer film, an interlayer film composed of a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a saponification degree of 98 mol% or more with n-butyraldehyde and a plasticizer is usually used ( See, for example, JP-A-56-82806).

This type of laminated glass has good weather resistance,
It has excellent properties such as good adhesiveness, no scattering of glass fragments, good transparency, and no optical distortion, but poor sound insulation. In particular, in the mid-high range near 2000 Hz, the sound insulation property is deteriorated by the coincidence effect.

The coincidence effect is a phenomenon in which when a sound wave is incident on glass, a transverse wave is conducted on the glass surface due to the rigidity and inertia of the glass, the transverse wave and the incident sound resonate with each other, and the sound is transmitted.

The demand for sound insulation is increasing more and more recently, and for example, as a window glass for a building, one which is always not affected by the change of the outside air temperature every season and exhibits excellent sound insulation performance is demanded.

As a sound insulating laminated glass, a laminated resin film including a plasticized polyvinyl butyral resin film and a resin film having a glass transition temperature of 15 ° C. or less such as a plasticized vinyl chloride-glycidyl methacrylate-ethylene copolymer resin film A method using an intermediate film is proposed (for example, see Japanese Patent Laid-Open No. 22974/1990).

[0008]

However, although this type of sound-insulating laminated glass has improved sound-insulating properties, since different kinds of resin films are laminated, the plasticizer of the resin film migrates over time. In addition, bleeding on the surface or interface of the resin film may cause optical distortion in the laminated glass, or the adhesiveness of the resin film may be deteriorated, so that the sound insulation performance may not be stably exhibited for a long period of time.

The present invention solves the above problems, and an object of the present invention is to take advantage of various excellent properties of an interlayer film made of a plasticized polyvinyl butyral resin and to reduce sound insulation due to a coincidence effect. Another object of the present invention is to provide an interlayer film for laminated glass and a laminated glass capable of preventing the above-mentioned problems and exhibiting sound insulation performance stably over a long period of time.

[0010]

The above object can be achieved by using the following interlayer film for laminated glass. That is, a laminated resin film of at least two layers consisting of two kinds of plasticized polyvinyl acetal resin films A and B, wherein the resin film A is polyvinyl alcohol having a saponification degree of 93 mol% or less with an aldehyde having 1 to 4 carbon atoms. The polyvinyl acetal resin (a) obtained by acetalization and a plasticizer, and the resin film B is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol having a saponification degree of 98 mol% or more with an aldehyde having 1 to 4 carbon atoms.
It consists of (b) and a plasticizer.

Moreover, in this case, is the amount of plasticizer of the resin film A larger than that of the resin film B?
Alternatively, as the resin film A and the resin film B, an intermediate film adhered via a transparent film that does not penetrate the plasticizer is used.

In the preparation of the polyvinyl acetal resins (a) and (b), the polyvinyl alcohol preferably has a degree of polymerization of 1000 to 3000. If the degree of polymerization is less than 1000, the penetration resistance of the laminated glass is reduced. On the contrary, when the degree of polymerization exceeds 3000, it becomes difficult to form the film.

For preparing the polyvinyl acetal resin (a), the saponification degree is 93 mol% or less, preferably the saponification degree 8
0 to 92 mol% of polyvinyl alcohol is used. Further, for the preparation of the polyvinyl acetal resin (b), polyvinyl alcohol having a saponification degree of 98 mol% or more, preferably a saponification degree of 99 mol% or more is used.

The saponification degree according to the present invention is determined according to JIS K672.
6 (polyvinyl alcohol test method), when polyvinyl alcohol having various saponification degrees is mixed, it is represented by the average saponification degree. The degree of polymerization also means the average degree of polymerization.

Further, the polyvinyl acetal resin (a) and
In the preparation of (b), as the aldehyde having 1 to 4 carbon atoms, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde and the like are used alone or in combination of two or more.

In particular, the polyvinyl acetal resin (a) and
(b) is preferably obtained by acetalizing with n-butyraldehyde having 4 carbon atoms. The above resin
In the preparation of (a) and resin (b), aldehydes other than the above-mentioned specific carbon number may be mixed and used within a range of 30% by weight or less.

The polyvinyl acetal resins (a) and (b) may be prepared by any known method. For example, polyvinyl alcohol is dissolved in warm water, the obtained aqueous solution is kept at a predetermined temperature, for example, 0 to 95 ° C., the required acid catalyst and aldehyde are added, and the acetalization reaction is allowed to proceed with stirring, Then, the reaction temperature is raised to complete the reaction by aging to complete the reaction, followed by neutralization, washing with water and drying to obtain powders of resin (a) and resin (b).

Here, the degree of acetalization is 60 in all cases.
~ 75 mol% is preferred. Acetalization degree is 60 mol%
When it is less than 1, the compatibility with the plasticizer becomes poor. On the contrary, it takes a long reaction time to obtain a resin having an acetalization degree exceeding 75 mol%, which is not preferable in the process. The degree of acetalization is measured based on JIS K6728 (polyvinyl butyral test method), for example.

The polyvinyl acetal resin (a) and the polyvinyl acetal resin (b) thus prepared are each mixed with a predetermined amount of a plasticizer, and the mixture is formed into a sheet by an extrusion method, a calender method, a pressing method or the like. Resin film A formed
And the resin film B is manufactured.

The thickness of each of the resin film A and the resin film B is preferably 0.05 mm or more. If the film thickness is less than 0.05 mm, it is not sufficient to exert good sound insulation performance and weather resistance. Also, the thicker the whole film, the better the sound insulation,
Practically, it is the same as the film thickness of a normal interlayer film for laminated glass, and is generally in the range of 0.3 to 1.6 mm.

As the plasticizer, known plasticizers used for this type of interlayer film, for example, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexoate, triethylene. Glycol dicaprylate, triethylene glycol di-n-heptate, tetraethylene glycol di-n-heptate and the like are preferably used.

Such a plasticizer is generally mixed in a predetermined amount within the range of 30 to 60 parts by weight with respect to 100 parts by weight of the resin (a) or the resin (b). Content of plasticizer is 3
If it is less than 0 part by weight, the penetration resistance of the laminated glass is lowered. On the contrary, if the content of the plasticizer exceeds 60 parts by weight,
The plasticizer oozes out, which adversely affects the adhesiveness of the laminated glass.

In the present invention, when the resin film A contains a larger amount of plasticizer than the resin film B,
The plasticizer amount of the resin film A is preferably in the range of 45 to 55 parts by weight, and the plasticizer amount of the resin film B is preferably in the range of 35 to 40 parts by weight. When the resin film A and the resin film B are adhered to each other through a transparent film that does not penetrate the plasticizer, the amount of the plasticizer in the resin film A and the resin film B is in the range of 35 to 50 parts by weight. preferable. In this case, the resin film A and the resin film B
The plasticizers are generally in the same amount, but different plasticizer amounts may be used.

In the present invention, when a transparent film that does not penetrate the plasticizer is used, the transparent film may be, for example, polyethylene terephthalate (PET).
Polybutylene terephthalate (PBT) is preferred. The thickness of these transparent films is generally 50-15.
Those having a thickness of 0 μm are used, and those having a surface treatment with a surface treatment agent such as a silane coupling agent or a metal alcoholate are preferable.

The resin (a) or the resin (b) is used as an interlayer film for laminated glass such as an ultraviolet absorber, a light stabilizer, an antioxidant, an adhesiveness adjusting agent, a surfactant and a coloring agent. Known additives may be added. In particular, in order to improve weather resistance, it is preferable that at least the resin film in contact with the glass plate contains an ultraviolet absorber or a light stabilizer.

The ultraviolet absorber is a benzotriazole type, for example, Tinuvin P manufactured by Ciba-Geigy.
(Product name), Tinubin 320 (Product name), Tinubin 32
6 (trade name), Tinuvin 328 (trade name), or a mixture thereof. Examples of the light stabilizer include hindered amine-based light stabilizers such as ADEKA STAB LA-57 (trade name) manufactured by Asahi Denka Co., Ltd.

Examples of the antioxidant include phenol compounds such as Sumilizer BHT (trade name) manufactured by Sumitomo Chemical Co., Ltd. and Irganox 1010 (trade name) manufactured by Ciba-Geigy.

Examples of the adhesion modifier include metal salts of carboxylic acids, for example, potassium salts and sodium salts of octylic acid, hexylic acid, butyric acid, acetic acid, formic acid and the like. Also,
Examples of the surfactant include sodium lauryl sulfate and alkylbenzene sulfonic acid.

To produce the interlayer film for laminated glass of the present invention, for example, film A / film B, film A / film B / film A, film B
/ Membrane A / Membrane B and a method of laminating and molding by pressing, or a method of laminating and molding each resin film by multilayer extrusion.

Further, for example, membrane A / transparent film / membrane B, membrane A / transparent film / membrane B / transparent film / membrane A,
A method of laminating and molding in the manner of membrane B / transparent film / membrane A / transparent film / membrane B by pressing, or a method of laminating and molding each resin film by multilayer extrusion is adopted.

In the interlayer film for laminated glass of the present invention, in particular, the resin film B is the outermost layer such as film B / film A / film B or film B / transparent film / film A / transparent film / film B. It is preferable to dispose it in terms of adhesion to glass and weather resistance.

In order to produce a laminated glass by using an intermediate film composed of at least two laminated resin films thus obtained, generally, the intermediate film is sandwiched between two transparent glass plates, and this is used as a rubber bag, for example. Pre-bonding is performed at about 70 to 110 ° C. while suctioning under reduced pressure, and then main bonding is performed in an autoclave at about 120 to 150 ° C. at a pressure of about 10 to 15 kg / cm ² . In this way, a sound-insulating laminated glass is manufactured.

Further, the resin film A and the resin film B, or the resin film A and the resin film B and the transparent film are superposed in a predetermined arrangement, and they are sandwiched between two transparent glass plates and heated and pressed to form an intermediate layer. A method in which film formation and laminated glass production are performed simultaneously is also adopted.

[0034]

A laminated resin film of at least two layers consisting of two types of plasticized polyvinyl acetal resin films A and B, wherein the resin film A contains polyvinyl alcohol having a saponification degree of 93 mol% or less and an aldehyde having 1 to 4 carbon atoms. A polyvinyl acetal obtained by acetalizing polyvinyl alcohol having a saponification degree of 98 mol% or more with an aldehyde having 1 to 4 carbon atoms. If it is composed of resin (b) and a plasticizer, sound energy is absorbed and
In the mid-high range around 000 Hz, the decrease in sound insulation due to the coincidence effect is prevented.

The reason for this is that when the laminated glass is bent and deformed by sound waves, energy loss is caused by shear deformation, especially at the interface between the resin films A and B, and that the resin film A
It is considered that since the glass transition temperature of 1 is lower than the glass transition temperature of the resin film B, the internal energy loss due to the deformation of the resin film itself increases effectively.

However, in this case, if the plasticizer contents of the resin films A and B are the same, the resin (a) of the resin film A becomes the resin film B.
Since the compatibility with the plasticizer is better than that of the resin (b), the plasticizer migrates from the resin film B to the resin film A over time, and the plasticizer bleeds to the surface or interface of the resin film, As a result, optical distortion may occur in the laminated glass, or the adhesiveness of the resin film may deteriorate.

Therefore, the amount of the plasticizer in the resin film A is changed to the resin film B.
If it is contained in a larger amount than the plasticizer amount of
Transfer of plasticizer between the two is suppressed. In addition, the resin films A and B
Even if the plasticizer contents of are the same, the resin films A and B are
If the plasticizer is adhered through a transparent film that does not penetrate, migration of the plasticizer between the resin films A and B is prevented.

[0038]

EXAMPLES Examples and comparative examples of the present invention will be shown below. Example 1 Preparation of Resin (a) and Resin Film A 193 g of polyvinyl alcohol (K217 manufactured by Kuraray Co., Ltd.) having a polymerization degree of 1700 and a saponification degree of 88.0 mol% was purified with 2 parts of pure water.
900 g was added and dissolved by heating. The temperature of this solution is 28
The temperature was adjusted to ° C, 201 g of 35% hydrochloric acid and 192 g of n-butyraldehyde were added, the liquid temperature was lowered to 2 ° C, and this temperature was maintained to precipitate the reaction product.

Then, the liquid temperature was maintained at 30 ° C. for 5 hours to complete the reaction, and the white powdery polyvinyl butyral resin (a) was prepared through neutralization, washing with water and drying. This resin
The degree of acetalization of (a) was 64.6 mol%.

100 parts by weight of the above resin (a) and 50 of triethylene glycol di-2-ethylbutyrate as a plasticizer.
The mixture was mixed with 1 part by weight, sufficiently melted and kneaded with a mixing roll, and press-molded with a press molding machine at 150 ° C. for 30 minutes to obtain a resin film A having a thickness of 0.2 mm.

Preparation of Resin (b) and Resin Film B 190 g of polyvinyl alcohol (117-BU manufactured by Kuraray Co., Ltd.) having a polymerization degree of 1700 and a saponification degree of 99.2 mol% was added to 2900 g of pure water and dissolved by heating. The temperature of this solution was adjusted to 20 ° C., 201 g of 35% hydrochloric acid and 124 g of n-butyraldehyde were added, the liquid temperature was lowered to 8 ° C., and this temperature was maintained to precipitate the reaction product.

Then, the liquid temperature was maintained at 50 ° C. for 4 hours to complete the reaction, and after neutralization, washing with water and drying, a white powdery polyvinyl butyral resin (b) was prepared. This resin
The degree of acetalization of (b) was 66.3 mol%.

100 parts by weight of the above resin (b) and 40 parts of triethylene glycol di-2-ethylbutyrate as a plasticizer.
1 part by weight, and the mixture is sufficiently melted and kneaded with a mixing roll, and the kneaded product is mixed with an ultraviolet absorber (Tinuvin P:
0.16 parts by weight of an antioxidant (Sumilyzer BHT: manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 part by weight of an adhesiveness adjusting agent (potassium acetate) were added and kneaded.

Thereafter, this kneaded product was subjected to a press molding machine for 15
The resin film B having a thickness of 0.2 mm was obtained by press molding at 0 ° C. for 30 minutes.

Manufacture of Intermediate Film and Laminated Glass The above resin films A and B were used, and these were laminated in the order of film B / film A / film B, and transparent float glass (vertical 3
0 cm × width 30 cm × thickness 3 mm), put this in a rubber bag and evacuate for 20 minutes under a vacuum of 20 mmHg, then transfer it to an oven at 90 ° C and degas at 30 ° C for 30 minutes.
It vacuum-pressed, holding for a minute.

The laminated glass pre-bonded in this manner was heated in an air autoclave at a temperature of 135 ° C. and a pressure of 1.
The main adhesion was carried out for 20 minutes under the condition of 2 kg / cm ² , and the formation of the intermediate film and the production of the laminated glass were simultaneously carried out.

With respect to this laminated glass, bleeding, optical distortion and sound insulation were evaluated by the following methods. The results are summarized in Table 1.

(1) Bleed A laminated glass having a width of about 5 mm was previously drawn on the surface of the resin film A with a black felt pen (magic ink) to prepare laminated glass, and the laminated glass was heated at 50 ° C. for 1 week. After standing, the degree of blurring of the drawn straight line was visually evaluated, and when no blur was observed, it was rated as O, and other cases were rated as Δ and X depending on the degree.

(2) Optical distortion: According to JIS R3212, the object in front is seen through the laminated glass, and the degree of distortion of the object is visually evaluated. Therefore, it was evaluated as Δ or ×.

(3) Sound insulation performance For laminated glass, the sound frequency (H
A graph showing the relationship between z) and the transmission loss (dB) was created, and the minimum transmission loss (TL value) near the sound frequency of 2000 Hz was obtained.

Example 2 The polyvinyl alcohol used in the preparation of the resin (a) in Example 1 was mixed with a polymerization degree of 2000 and a saponification degree of 80.0 mol%.
Polyvinyl alcohol (K420 made by Kuraray) 19
Changed to 3g. Other than that was performed like Example 1.
The results are summarized in Table 1.

Example 3 The polyvinyl alcohol used in the preparation of the resin (a) in Example 1 was mixed with a polymerization degree of 1700 and a saponification degree of 92.0 mol%.
Polyvinyl alcohol (Kuraray K217 and KS
I-C was mixed in a weight ratio of the former 0.45: the latter 0.55) to 193 g. Other than that was performed like Example 1. The results are summarized in Table 1.

Example 4 Resin films A and B prepared in Example 1 were prepared.
A 3% ligroin solution of tetrabutyl zirconate was applied to both sides of a transparent polyethylene terephthalate film (PET) having a thickness of 120 μm and dried at about 105 ° C. to prepare a surface-treated PET.

The above resin film A, resin film B and surface treatment P
Using ET, this is membrane B / treated PET / membrane A / treated PE
T / membrane B were superposed in this order, sandwiched from both sides by transparent float glass (length 30 cm × width 30 cm × thickness 3 mm), and in the same manner as in Example 1, the formation of an intermediate film and the production of laminated glass were carried out simultaneously. .

For this laminated glass, bleeding, optical distortion and sound insulation were evaluated in the same manner as in Example 1 by the following methods. The results are summarized in Table 1.

Example 5 In Example 4, instead of the surface-treated PET, the thickness 12
3% of tetrabutyl zirconate on both sides of 0 μm transparent polybutylene terephthalate film (PBT)
The surface-treated PBT obtained by applying the rebroin solution was used. Further, the amount of the plasticizer was changed to 45 parts by weight with respect to 100 parts by weight of the resin (a). Other than that was performed like Example 4. The results are summarized in Table 1.

Example 6 In Example 4, the surface-treated PET was replaced by a transparent polyethylene terephthalate film (PET) having a thickness of 120 μm which was not surface-treated. Other than that was performed like Example 4. The results are summarized in Table 1.

Comparative Example 1 The polyvinyl alcohol used in the preparation of the resin (a) in Example 1 was mixed with a polymerization degree of 1700 and a saponification degree of 94.0 mol%.
Polyvinyl alcohol (KSI-C manufactured by Kuraray Co., Ltd.) 1
It was changed to 93 g. Other than that was performed like Example 1. The results are summarized in Table 1. Comparative Example 2 In Example 1, only the resin film A was used without using the resin film B. However, the thickness of the resin film A was 0.76 mm.
Other than that was performed like Example 1. The results are summarized in Table 1.

Comparative Example 3 In Example 1, only the resin film B was used without using the resin film A. However, the thickness of the resin film B was 0.76 mm.
Other than that was performed like Example 1. The results are summarized in Table 1.

[0060]

[Table 1]

[0061]

As described above, in the present invention, the interlayer film of the laminated glass is a laminated resin film of at least two layers consisting of two kinds of plasticized polyvinyl acetal resin films A and B, and the resin film A is A polyvinyl acetal resin (a) obtained by acetalizing polyvinyl alcohol having a saponification degree of 93 mol% or less with an aldehyde having 1 to 4 carbon atoms and a plasticizer. The resin film B has a saponification degree of 98 mol% or more. Since it is composed of a polyvinyl acetal resin (b) obtained by acetalizing C. with an aldehyde having 1 to 4 carbon atoms and a plasticizer, sound energy is effectively absorbed, and a decrease in sound insulation due to the coincidence effect can be prevented. .

Moreover, the plasticizer amount of the resin film A is larger than that of the resin film B, or the resin film A
The resin film B and the resin film B are adhered to each other through a transparent film that does not penetrate the plasticizer, whereby the transfer of the plasticizer between the resin films A and B is suppressed, and stable sound insulation performance is exhibited over a long period of time. You can Further, there is an advantage that optical distortion of the laminated glass due to migration of the plasticizer can be prevented, and deterioration of adhesiveness of the resin film can be prevented.

Further, in the present invention, since the interlayer film of the laminated glass is composed of the plasticized polyvinyl acetal resin film having good transparency or the resin film and the transparent film which does not penetrate the plasticizer, it is resistant to impact penetration. Good, good adhesion between glass and interlayer film, glass fragments do not scatter when broken, transparency and excellent safety,
The weather resistance is also good.

Therefore, the interlayer film of laminated glass and the laminated glass of the present invention are particularly preferably used for window glass of buildings and the like which require high sound insulation performance.

Claims (3)

[Claims] 1. A laminated resin film of at least two layers comprising two types of plasticized polyvinyl acetal resin films A and B, wherein the resin film A contains polyvinyl alcohol having a saponification degree of 93 mol% or less and a carbon number of 1 to 4. Of polyvinyl acetal resin (a) obtained by acetalization with an aldehyde of (1) and a plasticizer, and the resin film B is obtained by acetalizing polyvinyl alcohol having a saponification degree of 98 mol% or more with an aldehyde having 1 to 4 carbon atoms. An interlayer film for laminated glass, comprising an acetal resin (b) and a plasticizer, wherein the resin film A contains more plasticizer than the resin film B. 2. A laminated resin film of at least two layers comprising two kinds of plasticized polyvinyl acetal resin films A and B, wherein the resin film A contains polyvinyl alcohol having a saponification degree of 93 mol% or less and a carbon number of 1 to 4. Of polyvinyl acetal resin (a) obtained by acetalization with an aldehyde of (1) and a plasticizer, and the resin film B is obtained by acetalizing polyvinyl alcohol having a saponification degree of 98 mol% or more with an aldehyde having 1 to 4 carbon atoms. An interlayer film for laminated glass, which comprises an acetal resin (b) and a plasticizer, and the resin film A and the resin film B are adhered to each other through a transparent film that does not penetrate the plasticizer. 3. The method according to claim 1, which is provided between two transparent glass plates.
Or laminated glass characterized in that the interlayer film for laminated glass according to 2 is adhered.